Plasticizing thermosetting resins



Patented Aug. 1Q, 1943 PLASTICIZING THERMOSETTING RESINS Paul C. Schroy, Stamford, Conn, assignor to American Cyanamid Company, N. Y., a corporation of Maine New York,

No Drawing. Application May 13, 1941,

. Serial No. 393,257

12 Claims. (01'. 260-33 This invention relates to improving the plasticity of a thermosetting resin and compositions containing such resins. It is particularly directed to improving the plasticity of urea-formaldehyde resins, phenol-formaldehyde resins, melamineformaldehyde resins, etc.

Various compounds have previously been suggested for use as plasticizers for thermosetting resins. Most of these plasticizers which have been used are compatible with thermosetting resins, such as urea-formaldehyde resins, only in limited proportions. For this reason, among others, the results have been somewhat unsatisfactory. 1

It is an object of this invention to improve the plasticity of thermosetting resins by means of substances which have good compatibility with the resins and which also improve the flow char-.

acteristics of the resins to a great extent.

Another object of this invention is to provide improved laminated materials bonded with thermosetting resins.

These and other objects are attained by blendmg with a desired thermosetting resin a small quantity of a substance containing the group x1lI-c,,n .-on where X is $03 or C and 11 and z are integers. Among the substances which contain this grouping are N-alkylol carboxylie acid amides, N-alkylcl sulfonamldes, N-alkylol imides.

A general formula for this group of compounds is the following:

. R-x-N-o,H,,-0H

where R. represents an organic radical, e. 3., alkyl, aryl, or aralkyl and R represents hydrogen, allwl, allslol, aryl, or an acyl group, and the.

other symbols are the sameas stated above. The compounds of this general typ may be produced in any suitable manner such as by the reaction of a sulionyl or carbonyl chloride with an alkylol amine, by the reaction of a carboxylic acid amide with an aldehyde, by the reaction of an lmide with an aldde, etc. The methylol and ethanol compounds are-easily produced and accordingly find wide application in practicing my invention. In the case or the methylol compounds y and z in the above formulae are l and z-respectively whereas in the ethanol compounds 2; and z are-2 and s respectively.

The N=methylol suliodes as well as the N- me lol m1: des and the N=methylol imides are the production of improved laminated'materials.

Thermosetting resins plasticized with the ethanol compounds of the type mentioned above exhibit many different properties from those plas ticized with the methylol compounds. Furthermore, the same plasticizer produces difierent effects on different thermosetting resins. Thus, in the production of laminated materialsutilizlng melamine-formaldehyde resins, the N-methylol s 9 suitable tor. use with 1.: $111 in laminating sheet is quite uniform sulfonamides are especially suitable as compared to the other N -alkylol compounds covered by the present invention.

The following example shown the use of these plasticizers in molding compositions, the proportions being given in parts by weight.

Example 1 A molding composition containing 30 to 40% sulflte pulp and from to 60% or a urea-formaldehyde resin together with an accelerator and a mold lubricant is blended with from 1 to 10% of p-toluene ethanol sulfonamide. This composition can be molded satisfactorily at pressures from 60-80% of those necessary when the plasticizer is not present. Furthermore, no "wet moldings are obtained.

Example 2 ating paper. is impreted with a ureathiourea-iormaldehyde resin syrup containing about to about 15%of N=methylol-p-toluene sulfonamide. The paper is dried to a volatile content of from about 3% to about 8% measured at about 150 C., and is stacked and pressed be= tweenplates at-about C., and at about 1500 pounds per square inch pressure. The resulting and has excellent resistance to water, acid and alkali. In making laminating sheets, it has been found that pressures of'only about 50% or those necessary without the presence of the plasticizer give equally good or superior results.

. Example 3 From about 1% to about 7%, preferably about 5%, oi. N-methylol phtliade is added to a. urea resin-cellulose molding composition, e.- on, a composition similar to that disclosed in Emmple l.

to about 15%, Preferably about I Excellent moldings were obtained from these compositions at pressures substantially less than those necessary without the added plasticizer- Furthermore, no sweating out. is observed.

Example 5 Excellent plasticizing action is observed if moldings be made according to Example 1 except that part of the urea resin is substituted with a melamine-formaldehyde resin, e. g., so that the weight ratio of resins is about 1:1.

Examples of other compounds which have been found suitable for use as plasticizers in the same used. Di-alkylol derivatives of the various amides, i-mides and sulfonamides may also be utilized in accordance with my invention. The eth-- anol derivatives may also be named as ethanolamines. Thus the N-p-toluene ethanol sulfonamide of Example 1 may be termed N-p-toluene sulfonyl ethanolamine.

While it is preferred that these plasticizers be used in concentrations ranging from about to about some of the more compatible members of the group may be used in concentrations up to or even more without undesirable results such as sweating out. The concentrations selected for any particular member of the group of plasticizers disclosed, will be dependent not only on the compatibility of that particular substance with the particular resin to be used, but also on the type of molding which is to be made from the resin composition. ,In general it has been found that about 5 to 10% of the plasticizer will give good results.

These new plasticizers have been found suitable for use with various thermosetting resins such as urea-formaldehyd resins, phenol-formaldehyde resins, melamine-formaldehyde resins, etc.- 0bviously various mixtures of these resins could be used. Furthermore, mixtures of urea, thiourea, or melamine could be used to form a composite resin with formaldehyde. Such composite resins One mol of toluene sulfonamide is reacted with one mol of formaldehyde (37% solution) which has previously been neutralized to a pH of bediethanol diphenyl disulfonamide may also be Example 7 To 261 parts (one mol) of monoethanolamine and 40 parts (one mol) of sodium hydroxide in a 25% aqueous solution, 144 parts (0.5 mol) of toluene-disulfonyl chloride are added slowly and with vigorous shaking. At the end of the. reaction, the solution is diluted with water to a concentration of about 10% with respect to the sodium hydroxide andthe' layer of liquid product is separated from the aqueous layer. To eliminate primary amine salts, the product is mixed with a dilute solution of formaldehyde and then neutralized to a pH of about 7 with sodium hydroxide. The sodium chloride which is formed is washed out with water and the product separated. The N,N -diethanol toluene disulfonamide is a clear, oily liquid which is readily compatible with urea resin syrup.

' Example 8 The same procedure as used in Example 7, is carried out with 102 parts (0.5 mol) of xylenesulfonyl chloride, 30.5 parts (0.5 mol) of monoethanolamine and 0.5 mol of sodium hydroxide.

The product obtained from this reaction is a liquid which is separated by a benzene extraction to give v N-ethanol-xylene sulfonamide.

formaldehyde to react with uncombined amine.

tween about 6.8 and 7.2 with triethanolamine.

-The reaction mixture is kept at a temperature of between about 20 C. and about 30 C. for about 12 hours, after which time the desired reaction is substantially complete. To avoid the formation of relatively incompatible resinous materials,

the reaction temperature should be controlled, and the pH should be kept nearly neutral, since excessive heat and strong acid or alkaline solution tend to catalyze resin formation. The product, N-meth'ylol toluene sulfonamide, is a clear,

' oily liquid compatible with urea resin syrups as indicated in Example 2. The reaction may be carried out in a suitabl solution, e. g., in an alcoholic solution.

Example 9 The same procedure as was used in Example 8 is carried out with a mixture of 190.5 parts (one mol) of p-toluene sulfonyl chloride with 61 parts (one mol) of monoethanolamine in the presence of one mol of sodium hydroxide (in 20% aqueous solution). The reaction product is treated with and then neutralized. After washing with water, the product, p-toluene-ethanol sulfonamide, is separated oi as an oily liquid containing some water (about 15%).. This substance is com-' patible with urea-formaldehyde resins as indicated in Example 1.

Example 10 121 parts of benzamide (preferably substantially free from ammonium benzoate), slurried into 121 parts of isopropyl alcohol, are added to 162 parts of aqueous formaldehyde (37%) which has been previously neutralized with 3.4 parts of triethanolamine. On reacting at 40 to 50 C. for 30 to 60 minutes, the benzamide becomes soluble. The resulting product is separated and is compatible with urea and thiourea resin syrups as indicated in Example 3.

. Example 11 I I To 147 parts of phthallmide slurried in 147 parts of isopropyl alcohol are added 81 parts of aqueous formaldehyde (37%) which has been previously neutralized with 1.7 parts of triethanolamine. On warming to 40- 50 C., the flakes changed to a fine granular product, N- methanol phthalimide. An excess of neutralized aqueous formaldehyde was added and the mixture allowed to stand overnight at room temperature.

The product is then separated and may be utilized in the manner illustrated in Example 4.

From the above examples it will be seen that there are at least two general methods which and the pH kept within certain ranges, resinous or other polymerized reaction products will tend to form instead of the desired product. For example, in the reaction of p-toluene sulfonamide with .formaldehyde, the temperature should not 5 exceed 40 C. as otherwise some of the nearly insoluble oily reaction products, probably the methylene derivatives, begin to form. Likewise the pH of the reaction mixture shouldb kept within the limits of approximately 5-8.

Although the invention is not to be considered as limited by any theoretical explanations, the various reactions described below may serve to give a better understanding of the present invention. They may also furnish a possible explanation of the high degree of compatibility of these new plasticizers and the excellent properties of the products containing them.

The structural formula for the resinous reaction product of CH3.C6H4.SO2.NH2, for example,-

with HCHO, according to Hug, Bull. Soc. Chim. 51, 990 (1934); Chem. Abs. 29, 752 (1935), is

CH3 CH3 CH:

whereas the improved plasticizer formed by the reaction of these same two materials as in Ex ample 5 has the structural formula the following manner;

where Xrepresents S02 or CO. The reaction would be similar with the hydroxyl group of a phenolic or other similar resin. There is a possibility that there might also be a reaction between the alkylol acid amide and the hydroxyl groups of the cellulosic filler, if such a filler be used.

These new plasticizing compounds have the advantage that they do not adversely affect theflnlsh, strength, or water resistance of the resin in which they are incorporated. These compounds may be used either singly or mixed. They may be mixed with the molding powders or with the resin syrup. By the use of these plasticizers a decided improvement in the molding is obtained. The molding pressures necessary may be only one half the previously necessary value,

enabling the molding of more complex shapes or larger pieces without any increase in the size of the press. Furthermore, because of the good compatibility, no sweating out occurs. This has been one of the outstanding difficulties with prior plasticizers. The improved molding property is particularly noticed with relatively large moldings having a long draw, such as cabinets, etc. These plasticizers are also of great value for use in the production of translucent laminated products for lighting and sign applications.

This application is a continuation-in-part of my copending application Serial No. 266,135, entitled Elasticized thermosetting resins and filed April 5, 1939.

Any suitable changes may be made without departing from the spirit and scope of my invention as defined in the appended claims.

I claim:

1. A formaldehyde-urea molding composition 30 comprising N, p-toluene-sulfonyl ethanolamine 40 sulfonamide asa plasticizer.

5. A homogeneous composition comprising a urea-formaldehyde resin and a N-ethanol sulfonamide as a plasticizer.

6. A homogeneous composition comprising at least one thermosetting resin, a filler and from about A;% to about 15% of a N-ethanol sulfonamide as a plasticizer.

7. A method of increasing the plasticity of a a thermosetting resin which comprises adding a small quantity of a N-ethanol sulfonamide as a plasticizer.

8. A process of increasing the plasticity of a molding composition including a urea-formaldehyde resin and a filler comprising adding to such a composition a compatible N-ethanol sulfonamide.

9. A homogeneous composition comprising a urea-formaldehyde resin, a filler andirom about /z% to about 15% of a N-ethanol sulfonamide as a plasticizer.

10. A homogeneous composition comprising a melamine-formaldehyde resin, a filler and from about to about 15% of a N-ethanol sulfonamide as a plasticizer.

11. A homogeneous composition comprising a melamine-formaldehyde resin and N, p-toluene sulfonyl ethanolamine as a plasticizer.

12. A homogeneous composition comprising a urea-formaldehyde resin, a melamine-formaldehyde resin and a N-ethanol sulfonamide as a plasticizer.

PAUL C. SCHROY. 

